Synthetic resin and method of producing



Patented a, 1931 i um'rsofsraras- PATEN'l- OFFICE Hercules PowderCompany, Wilmington, ,DeL, a corporation of Delaware No Drawing.

Application January 12, 1935, Serial No. 1,499

is Claims. (01. 260-8) This invention relates to a newcomposition ofmatter and method for its production. I In accordance with thisinvention a novel synthetic resin, having'characteristics rendering itvaluable for use variously in the commercial arts,

is prepared .by reacting together ,dipentene, maleic anhydride and rosinor abietic acid. 'The reace tion involved is probably explained on thebasis.

of the unsaturated bond of the malelc anhydride 10 reacting with theunsaturated-bonds of the dipentene and the abietic acid, The new com-'-position is a highly acidic material of complex nature.

In preparing the synthetic resin in accordance with my inventionthereagents may be reacted in widely varying proportions dependin uponthe physical characteristics desired for th resin product withconsideration to the use to which T it s to be put. Generally speaking,it is desir- 2o able to employ maleic anhydride approximately in theproportion necessary to completely satisfy #the reactivity of thedipentene and the abietic acid. Thus, for example, with use ofrelatively large amounts of dipentene, the product is soft and tough,with more abietic acid in proportion to dipentene, the product is hardand brittle, and I so on, it being clear that by varying the proportionsand amounts of the reagents products having varying characteristics maybe produced. As

illustrative, for example, dipentene may be used.

within therange 0.1 to 0.9 moles, maleic anhydride within about therange0.2 to 2.0 moles and agietic acid withinabout the range '0.1 to 0.9moles.

Dipentene comprises the major portion of a terpene icut boiling withinthe range l70-178 C. obtained by fractionation of crude turpentine fromthe Pinus palustris, and this terpene cut may be used in place of puredipe'ntene'wlthin 40 the scope of'this invention. However, it ispreferred to use a pure dipentene boiling at 174.5-

177.5 C., which may beobtainedas a middle out between pine oil andturpentine.

' In preparing the improved synthetic resin the 5 reagents'will bereacted in the presence of heat However, it will be expressly understoodthat any means for efiecting the reaction is contemplated as within thescope of this invention. Any suitable temperature may be used, though a.temperature within the range (say) about l25-250 C. is desirable. Thereaction will usually be carried out under atmospheric pressure, butwith variations of temperature procedure under reduced or super-pressurewill obviou ly be within the scope of my invention. The production ofthe resin in accordance with-this invention may be carried out in anysuitable apparatus, as any suitable container in which the reagents maybe heated. On completion-of the reaction any volatile-unreacte'd mattermay be removed or sep-.

arated from the product by the application of a vacuumto thereaction'mass before cooling.

its a specific illustration, for example, parts byweight of dipentene,165 parts of abietic acid and 98 parts of maleic anhydride are heatedtogether at a temperature of approximately 200 C. for about 3 hours. Thepressure on the re action mass is then reduced to about 15 mm. of

mercury and any unreacted maleic anhydride and the lnertingredientsassociated with the dipentene are distilled oil.

.The reaction product obtained by the above procedure will be found tohave a direct acid number of about 230, saponification value of r about414. melting point (drop method) of about 95 C. and a-rhodanometriciodine value of 23.1. Asuillustrative of various amounts of the severalreagents which may be reacted to produce resins in accordance with thisinvention, for example the reagents may be reacted in the variousproportions given in the following table:

Maleic Dipenteue Rosin anhydride Parts 1 -Paris by Paris, by weightweigh weight The several reagents in, for example, the proportion givenin the above table may be reacted in any suitable container, at atemperature (say) within the range of ($250 0. .for (say) one to livehours. Volatile unreacted matter may, as has been indicated, be removedon completion of thereaction by reducing the pressure in the reactionmass before cooling.

The product in accordance with this invention will be found to be ahighly acidic resin, capable, for example, of reacting with alcohols,as, for example, polyhydric alcohols as glycerol, aliphatic glycols,etc., to yield synthetic gums or resins whichlhave characteristicsmaking them highly desirable for'use, for example, in 'varnishes,lacquers, etc., etc.

As an example of the esterificatlon of the product obtained'in thespecific illustration above with a polyhydric alcohol the following isillusicalsuch' as, for example, esters of abietic acid] trative: about.100 parts by weight of any or the abovereaction products and 58 parts ofglycerol are heatedfiiat a temperature of-200 C. for 6 hours followed byheatingmt 250 C. iortone hour. The resulting resin has an acid number of30 and 'a melting point (drop method) of' approximately. 113 -C. It ishighly desirable, for

use in lacquers-and varnishes. I Drying or semidrying oils or theiracids may be added.-

Esterification with monohydric alcohols, as methyl, ethyl, butylalcohols, etc., may likzfiyise be carried out, in the'case or lowboiling cohols preferably under pressure.

It'will be understood that in producing the compositions comprising thisinvention abietic'acid as such may be used or rosin,- either wood orgum, preferably high in abieticacid content may be used equivalently.

It is also contemplated to use in place of abietic acid other compoundscontaining the abietylrade with monohydric; or polyliydric alcohol asmethyl,

ethyl, propyl alcohols, glycol, glycerol, etc. When an ester of 'abieticacid'is employed, the acidity of the reaction product; is lower due tothe fact that one carboxyl group is esterifled.

vl- As a specific illustration, for example or theuse of an ester ofabietic acid, 100 parts by weight of dipentene, 158 parts of methylabietate and 98 parts of maleic anhydride are heated together at atemperature of about 200C. for three hours. The pressure is then reducedto 15 mm; of mercury and theexcess of, maleic anhydride and the productiof an alcohol and an acidic composition comprising a reaction productof the reaction of dipentene, maleic anhydride and a compound containingthe abietyl radical. J K

2. A synthetic resin comprising a reaction product of an alcohol and anacidic composition comprising a reaction product of the reaction ofdipentene, maleic. anhydride and abietic acid.

3.-A synthetic resin comprising a reaction product of an alcohol and anacidic composition I comprising areaction product'of the reaction ofdipentene, maleic anhydride and an abietic acid ester.

' .4; A 'synthetic resin comprising a reaction product of an, alcoholand an acidic composition comprising a' reaction product of the reactionof dipentene, maleic anhydride and rosin.

5. A synthetic. resin comprising a reaction product of apolyhydricalcohol and an acidic composition comprising a reaction product of thereaction of dipentene, maleic anhydride and a. compound containing theabietyl radical.

6. A synthetic resin comprising a reaction composition comprising areaction product of the reaction of dipentene, maleic anhydride and acompound, containing the abietyl radical.

7. A synthetic resin comprising -a reaction product of glycerol and anacidic composition comprising .acre'action product of the reaction ofdipentene, maleic anhydride andia compound containing the abietylradical.

8. A synthetic resin comprising a reaction product of an aliphaticglycol and an 'acidic composition comprising a reaction product of thereaction of-dipentene, maleic anhydride and a compound containing theabietyl radical.

' 9; A synthetic resin comprising a reaction product of ethyl alcoholandan acidic composition comprising a reaction product ofthe re-' actionofrdipentene, maleic'anhydride and a compound containing the abietylradical.

10. A synthetic resin produced by combining a polyhydric alcohol, adrying oil fatty acid, and a reaction product formed by combiningdipentene,

maleic anhydride and a compound containing the abietyl radical.

11. The method for producing asynthetic resin which includes reactingdipentene, maleic anhy dride and a compound containing the abietylradical and of a character such that the abietyl radical is availablefor reaction, and then'reacting the product of said reaction with analcohol. 1 2. 'The method for producing a synthetic resin which includesreacting dipentene, maleic anhydride and abietic acid and then reactingthe product of said reaction with an alcohol.

i 13.- The method for producing a synthetic resin 'which includesreacting dipentene, maleic anhydride and an ab'ietic acid ester of acharacter such that the abietyl radical is available for reaction andthen reacting the product of said reaction with an alcohol.

14. The method for producing a synthetic resin 'which includes reactingdipentene, maleic anhyg product of a monoh'ydric alcohol ,and an acidicdride and rosin and then reacting the product of 1 said reaction-with analcohol.

- 15. A coating composition comprising a reaction product of an alcoholand an acidic composi tion formed from dipentene, maleic anhydride andacompound containing the abietyl radical, and a solvent. I

I 16. A coating composition comprising a reaction product of an alcoholand an acidic composi-m tio'n formed from dipentene, maleic anhydrideand a compound containing-.the abietyl-radical, a non-volatile lacqueringredient and a solvent.

.17. A coating composition comprisinga reaction product of an alcoholand an acidic composition formed from dipentene, maleic anhydride and acompound containing the abietyl radical,-

a non-volatile varnish ingredient and a solvent.

18. A synthetic. resin K'comprising'a reaction product of an alcohol andan acidic compositioncomprising'a reaction product of the reactionof aterpene cut boiling'within the range -178- C.,.maleic anhydride and acompound containing the abietyl radical.

- H. COBURN.

